CN116060074A - Catalytic carrier for electrochemical reaction and preparation method thereof - Google Patents

Catalytic carrier for electrochemical reaction and preparation method thereof Download PDF

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CN116060074A
CN116060074A CN202111284818.7A CN202111284818A CN116060074A CN 116060074 A CN116060074 A CN 116060074A CN 202111284818 A CN202111284818 A CN 202111284818A CN 116060074 A CN116060074 A CN 116060074A
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carrier
transition metal
carbon
nitrogen
source
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杨惟翔
李强
潘光彩
唐琪雯
周卫江
陈启章
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Sinocat Environmental Technology Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to the technical field of electrocatalysis of nano-carrier material modifiers, in particular to a catalytic carrier for electrochemical reaction and a preparation method thereof. The catalytic carrier takes nano carrier material as a core and doped carbon as a shell; the doped carbon contains at least one of transition metal, nitrogen, sulfur and phosphorus. The carbon is doped as a shell, so that the carrier with a core-shell structure is prepared, and the stability, conductivity and catalytic activity of the carrier in acid-base and electrochemical environments are improved. The chemical stability is close to graphitized carbon, the physical stability is close to oxide carrier, the conductivity is the same order of magnitude as graphitized carbon, and the catalyst has a certain oxygen reduction electrocatalytic activity.

Description

Catalytic carrier for electrochemical reaction and preparation method thereof
Technical Field
The invention relates to the technical field of electrocatalysis of nano-carrier material modifiers, in particular to a catalytic carrier for electrochemical reaction and a preparation method thereof.
Background
In the field of electrocatalysis (such as oxygen electrochemical reduction reaction, electrolytic water oxygen evolution reaction and electrolytic water hydrogen evolution reaction), the catalyst and its carrier are required to have good chemical stability, electrochemical stability, mechanical stability and higher conductivity in acid (alkali) environment, and along with the rapid development of various new energy technologies such as clean energy market becoming larger and larger in recent years, the carrier of the catalyst for electrochemical reaction also puts higher requirements, for example, the electrode catalyst carrier is required to have certain catalytic activity, and the electrode catalyst carrier and the active center of the main catalyst complement each other to cooperate with each other to improve the performance of the electrode catalyst or other electrode materials. In general, conventional nanocarrier materials are either stable (e.g., al) under electrochemical conditions and acidic (basic) properties 2 O 3 ) Is not ideal or has poor electrical conductivity (e.g. TiO 2 Or the like), or does not possess catalytic activity (e.g., carbon black), and does not meet the higher requirements of current electrocatalytic supports.
In summary, the stability, conductivity and catalytic activity of the current electrode catalyst carriers for fuel cells, metal-air cells and electrolytic cells are difficult to meet the carrier requirements at the same time.
Disclosure of Invention
The invention aims at: aiming at the problem that the existing catalyst carrier in the prior art is difficult to meet the requirements of stability, conductivity and catalytic activity, the catalytic carrier is provided, the nano carrier material is used as an inner core, the doped carbon is used as a shell, and the carrier with a core-shell structure is prepared, so that the stability, conductivity and catalytic activity of the carrier in acid-base and electrochemical environments are improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a catalytic support having a nano-support material as a core and doped carbon as a shell; the doped carbon contains at least one of transition metal, nitrogen, sulfur and phosphorus. The catalytic carrier is of a core-shell structure.
As a preferred embodiment of the present invention, the nanocarrier material comprises Al 2 O 3 Carbon, siO 2 、TiO 2 、SnO 2 、ATO、SiC、ZrO 2 One of the following; or Al 2 O 3 Carbon, siO 2 、TiO 2 、SnO 2 、ATO、SiC、ZrO 2 A mixture of several of these; or Al 2 O 3 Carbon, siO 2 、TiO 2 、SnO 2 、ATO、SiC、ZrO 2 A composite nanomaterial formed by compounding several of the above materials.
As a preferable embodiment of the present invention, the transition metal is at least one of Fe, co, ni, cu.
As a preferred embodiment of the present invention, in the doped carbon, the molar ratio of each element is: transition metal: nitrogen: sulfur: phosphorus = 100-30:0-20:0-30:0-10:0-10. At least one of the contents of transition metal, nitrogen, sulfur and phosphorus is not 0.
A preparation method of a catalytic carrier comprises the following steps,
s1, coating, namely preparing a nano carrier material coating material, wherein the coating material comprises a carbon source and at least one of a transition metal source, a nitrogen source, a sulfur source and a phosphorus source; coating the coating material on the surface of the nano carrier material to obtain a composite material;
s2, pyrolyzing, heating the composite material to carbonize a shell layer, and obtaining the catalytic carrier.
As a preferable scheme of the invention, the coating material coats the surface of the nano-carrier material in a complexing, polymerization or adsorption mode.
As a preferable scheme of the invention, the carbon source is a carbon-containing organic small molecule, the nitrogen source is a nitrogen-containing organic small molecule, the sulfur source is a sulfur-containing organic small molecule, the phosphorus source is a phosphorus-containing organic small molecule, and the transition metal source is a transition metal-containing organic small molecule or a transition metal inorganic salt or a transition metal organic salt.
As a preferred embodiment of the present invention, the small organic molecule containing a transition metal includes at least one of iron phthalocyanine, cobalt phthalocyanine, iron porphyrin, cobalt porphyrin; the transition metal inorganic salt comprises FeCl 3 、CoCl 2 、NiCl 2 、CuCl 2 、Fe(NO 3 ) 3 、Co(NO 3 ) 2 、Ni(NO 3 ) 2 、Cu(NO 3 ) 2 At least one of (a) and (b); the transition metal organic salt comprises at least one of ferric acetylacetonate, ferrous acetate, ferric acetate, ferrocene, cobalt acetylacetonate, cobalt acetate, nickel acetylacetonate and nickel acetate.
As a preferred embodiment of the present invention, the small carbon-containing organic molecule or the small nitrogen-containing organic molecule includes at least one of aniline, pyridine, pyrrole, 2, 6-diaminopyridine, and dopamine.
As a preferred embodiment of the present invention, the composite material is washed and dried before step S2.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
the catalytic carrier of the invention takes the nano carrier material as an inner core and takes the doped carbon as a shell to prepare the carrier with a core-shell structure, thereby improving the stability, conductivity and catalytic activity of the carrier in acid-base and electrochemical environments. The chemical stability is close to graphitized carbon, the physical stability is close to oxide carrier, the conductivity is the same as the graphitized carbon in quantity, and the catalyst has M-N-C catalytic activity.
The invention provides a method for preparing the catalytic carrier by tightly coating transition metal nitrogen-doped carbon on the surface of a nano carrier material. Organic small molecules containing nitrogen, carbon, sulfur and phosphorus are selected as raw materials and coated on the surface of the nano carrier material in a complexing or polymerization mode; the transition metal source adopts transition metal inorganic salt or transition metal organic salt to carry out complexation reaction with organic micromolecules of the nitrogen source carbon source in a complexation mode. After the polymerization reaction of small organic molecules of nitrogen, carbon, sulfur or phosphorus, a macromolecule or a macromolecular compound is formed to be coated on the surface of the nano carrier material, so that a compact and complete coating shell structure is formed. If necessary, multiple coating and carbonization are adopted; or repeating the coating and carbonization for a plurality of times to obtain a tightly-packed and complete shell structure.
Drawings
FIG. 1 is a TiO according to example 1 of the present invention 2 TEM image of @ Co-N-C.
FIG. 2 is TiO 2 、TiO 2 LSV Curve of @ Co-N-C, co-N-C sample in 0.1MNaOH (load 150. Mu.g/cm 2 ) Comparison graph.
FIG. 3 is a LSV curve of the samples prepared in the examples in 0.1M NaOH (electrode surface catalyst loading 150. Mu.g/cm) 2 ) Comparison graph.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
TiO 2 The nanoparticle is a core and the doped carbon containing cobalt and nitrogen is a shell.
The nano carrier material is TiO 2 A nanoparticle; the coating material is 2, 6-Diaminopyridine (DAP) or CoCl 2 Ammonium persulfate.
The preparation process is as follows:
s1 coating, taking 108mgTiO 2 Nanoparticle, 108mg of 2, 6-Diaminopyridine (DAP) and 6.45mg of CoCl 2 Add to 30mL of deionized water and ultrasonically disperse for 30 minutes (min) to prepare mixture A. Solution B was prepared by dissolving 228mg of Ammonium Persulfate (APS) in 15mL of deionized water. Solution B was added dropwise to mixture A and stirring was continued at room temperature (25 ℃ C.) for 4Hours. The mixture was suction-filtered with deionized water until the filtrate conductivity was less than 10. Mu.S/cm, and washed twice with absolute ethanol. The product was dried in a vacuum oven (80 ℃) for 12h.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace.
And (3) taking the obtained powder as a core, and repeating the step S1 and the step S23 times to obtain the titanium oxide carrier which is tightly and completely wrapped by the carbon layer containing cobalt and nitrogen. The prepared sample is marked as TiO 2 @Co-N-C(DAP)。
The TEM image is shown in fig. 1.TiO (titanium dioxide) 2 、TiO 2 LSV Curve of @ Co-N-C, co-N-C sample in 0.1MNaOH (load 150. Mu.g/cm 2 ) Such as shown in fig. 2. Testing of TiO 2 、TiO 2 Conductivity of @ Co-N-C, ketjen EC300J samples at 20MPa, test results are shown in the following table.
TABLE 1 TiO 2 、TiO 2 Conductivity of @ Co-N-C, ketjen EC300J sample at 20 MPa.
Sample name Testing pressure intensity Conductivity of
TiO 2 20MPa 5.4×10 -3 S/cm
TiO 2 @Co-N-C 20MPa 2.7×10S/cm
Keqin EC300J 20MPa 5.4×10S/cm
As shown in FIG. 1, co-N-C successfully completed TiO 2 Wrapping with TiO to form 2 The core-shell structure takes the core Co-N-C as the shell. After Co-N-C coating, compared with TiO before coating 2 The conductivity is greatly improved. As shown in Table 1, tiO 2 The conductivity was only 5.4X10 before Co-N-C coating -3 S/cm, after coating Co-N-C on the surface of the catalyst, tiO 2 The conductivity of the @ Co-N-C is improved by 4 orders of magnitude and increased to 2.7X10S/cm, which is similar to the conductivity of the KetEC 300J (5.4X10S/cm).
As shown in FIG. 2, co-N-C coated TiO 2 Compared with TiO before coating 2 The catalytic activity is greatly improved. TiO (titanium dioxide) 2 Initial potential of @ Co-N-C sample in 0.1MNaOH (0.82V RHE ) And 0.4V RHE Corresponding current density (2.56 mA/cm) 2 ) Relative to TiO 2 Is (0.62V) RHE ) And current density (0.78 mA/cm) 2 ) Increases by 200mV and 2.3 times, and is close to the activity of Co-N-C (initial potential: 0.84V RHE ,3.07mA/cm 2 )。
Example 2
Al 2 O 3 The nanoparticle is a core and the doped carbon containing cobalt and nitrogen is a shell.
The nano carrier material is Al 2 O 3 A nanoparticle; the coating material is dopamine hydrochloride and CoCl 2 。
The preparation process is as follows:
s1 coating, taking 108mgTiO 2 The nanoparticles were dispersed in 30mL deionized water by sonication for 30min to prepare mixture a. 189.64mg of dopamine hydrochloride was dissolved in 10mL of ultrapure water, and added to the mixture A, followed by stirring for 30 minutes. The ph=8.5 was adjusted using Tris buffer solution and stirring was continued for 1h at room temperature (25 ℃). Then 6.45mgCoCl 2 Dissolved in5mL of ultrapure water was slowly added dropwise to the above solution and stirring was continued for 30min. The resulting mixture was centrifuged and dried in a vacuum oven (80 ℃ C.) for 12 hours.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace. The catalyst prepared was designated as TiO 2 @Co-N-C (dopamine).
Example 3
TiO 2 The nanoparticle is a core and the doped carbon containing cobalt and nitrogen is a shell.
The nano carrier material is TiO 2 A nanoparticle; the coating material is aniline, coCl 2 Ammonium persulfate.
The preparation process is as follows:
s1 coating, taking 108mgTiO 2 Nanoparticles, 93mg (2.6 mL) aniline solution and 6.45mg CoCl 2 Add to 30mL of deionized water and ultrasonically disperse for 30 minutes (min) to prepare mixture A. Solution B was prepared by dissolving 228mg of Ammonium Persulfate (APS) in 15mL of deionized water. Solution B was added dropwise to mixture A and stirring was continued at room temperature (25 ℃) for 4 hours. The mixture was suction-filtered with deionized water until the filtrate conductivity was less than 10. Mu.S/cm, and washed twice with absolute ethanol. The product was dried in a vacuum oven (80 ℃) for 12h.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace. The catalyst prepared was designated as TiO 2 @Co-N-C (aniline).
Example 4
Al 2 O 3 The nanoparticle is a core and the doped carbon containing cobalt and nitrogen is a shell.
The nano carrier material is Al 2 O 3 A nanoparticle; the coating material is 2, 6-Diaminopyridine (DAP) or CoCl 2 Ammonium persulfate.
S1 coating, taking 108mgAl 2 O 3 Nanoparticle, 108mg of 2, 6-Diaminopyridine (DAP) and 6.45mg of CoCl 2 30mL of deionized water was addedIn water, the mixture A was prepared by ultrasonic dispersion for 30 minutes (min). Solution B was prepared by dissolving 228mg of Ammonium Persulfate (APS) in 15mL of deionized water. Solution B was added dropwise to mixture A and stirring was continued at room temperature (25 ℃) for 4 hours. The mixture was suction-filtered with deionized water until the filtrate conductivity was less than 10. Mu.S/cm, and washed twice with absolute ethanol. The product was dried in a vacuum oven (80 ℃) for 12h.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace.
And (3) taking the obtained powder as a core, and repeating the step S1 and the step S23 times to obtain the alumina carrier which is tightly and completely wrapped by the carbon layer containing cobalt and nitrogen. The prepared sample is marked as Al 2 O 3 @Co-N-C(DAP)。
Al 2 O 3 The carbon material is easy to dissolve in an acid solution, the surface of the carbon material is coated with compact doped carbon material to improve the stability of the carbon material, and the experiment is carried out through Al 2 O 3 、Al 2 O 3 The percent mass loss after 5 hours of reaction of Co-N-C (DAP) and Co-N-C in 3MHCl solution was compared to evaluate the stability of the material under acidic conditions and the test results are shown in the following table.
TABLE 2 Al 2 O 3 、Al 2 O 3 Total amount of Co-N-C (DAP) and Co-N-C dissolved in 3MHCl for 5 hours.
Sample name Total amount of 5 hr dissolution (%)
Al 2 O 3 83％
Al 2 O 3 @Co-N-C(DAP) 8％
Co-N-C 2％
As can be seen from Table 2, the Co-N-C material has a good stability under acidic conditions, and the mass loss after 5 hours of reaction in 3MHCl is only 2%, however Al 2 O 3 The mass loss under the same conditions is 83%, and the alumina carrier Al is tightly and completely wrapped by a carbon layer containing cobalt nitrogen 2 O 3 The mass loss of the @ Co-N-C (DAP) is only 8%, so that the carbon layer on the surface of the alumina can play a role in protecting and improving the stability of the carrier.
Example 5
Carbon (ketjen black) is the core and doped carbon containing cobalt and nitrogen is the shell.
The nano carrier material is ketjen carbon black; the coating material is 2, 6-Diaminopyridine (DAP) or CoCl 2 Ammonium persulfate.
S1 coating, taking 108mg of ketjen black, 108mg of 2, 6-Diaminopyridine (DAP) and 6.45mg of CoCl 2 Add to 30mL of deionized water and ultrasonically disperse for 30 minutes (min) to prepare mixture A. Solution B was prepared by dissolving 228mg of Ammonium Persulfate (APS) in 15mL of deionized water. Solution B was added dropwise to mixture A and stirring was continued at room temperature (25 ℃) for 4 hours. The mixture was suction-filtered with deionized water until the filtrate conductivity was less than 10. Mu.S/cm, and washed twice with absolute ethanol. The product was dried in a vacuum oven (80 ℃) for 12h.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace.
And (3) taking the obtained powder as a core, and repeating the step S1 and the step S23 times to obtain the carbon carrier which is tightly and completely wrapped by the carbon layer containing cobalt and nitrogen. The prepared sample was labeled C@Co-N-C (DAP).
Example 6
SiC nanoparticles are cores and doped carbon containing cobalt and nitrogen is a shell.
The nano carrier material is SiC nano particles; the coating material is 2, 6-Diaminopyridine (DAP) or CoCl 2 Ammonium persulfate.
S1 coating, taking 108mg of SiC nano particles, 108mg of 2, 6-Diaminopyridine (DAP) and 6.45mg of CoCl 2 Add to 30mL of deionized water and ultrasonically disperse for 30 minutes (min) to prepare mixture A. Solution B was prepared by dissolving 228mg of Ammonium Persulfate (APS) in 15mL of deionized water. Solution B was added dropwise to mixture A and stirring was continued at room temperature (25 ℃) for 4 hours. The mixture was suction-filtered with deionized water until the filtrate conductivity was less than 10. Mu.S/cm, and washed twice with absolute ethanol. The product was dried in a vacuum oven (80 ℃) for 12h.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace.
And (3) taking the obtained powder as a core, and repeating the step S1 and the step S23 times to obtain the silicon carbide carrier which is tightly and completely wrapped by the carbon layer containing cobalt and nitrogen. The prepared sample was labeled SiC@Co-N-C (DAP).
Example 7
TiO 2 The nanoparticle is a core and the doped carbon containing cobalt and nitrogen is a shell.
The nano carrier material is TiO 2 A nanoparticle; the coating material is 2, 6-Diaminopyridine (DAP) or FeCl 3 Ammonium persulfate.
The preparation process is as follows:
s1 coating, taking 108mgTiO 2 Nanoparticle, 108mg of 2, 6-Diaminopyridine (DAP) and 8.11mg of FeCl 3 Add to 30mL of deionized water and ultrasonically disperse for 30 minutes (min) to prepare mixture A. Solution B was prepared by dissolving 228mg of Ammonium Persulfate (APS) in 15mL of deionized water. Solution B was added dropwise to mixture A and stirring was continued at room temperature (25 ℃) for 4 hours. Filtering and washing the obtained mixture with deionized water until the electric conductivity of the filtrate is less than 10 μS/cm, and thenWashing twice with absolute ethanol. The product was dried in a vacuum oven (80 ℃) for 12h.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace.
And (3) taking the obtained powder as a core, and repeating the step S1 and the step S23 times to obtain the titanium oxide carrier which is tightly and completely wrapped by the carbon layer containing iron and nitrogen. The prepared sample is marked as TiO 2 @Fe-N-C(DAP)。
Example 8
TiO 2 The nanoparticle is a core and the doped carbon containing cobalt and nitrogen is a shell.
The nano carrier material is TiO 2 A nanoparticle; the coating material is 2, 6-Diaminopyridine (DAP) or NiCl 2 Ammonium persulfate.
The preparation process is as follows:
s1 coating, taking 108mgTiO 2 Nanoparticle, 108mg of 2, 6-Diaminopyridine (DAP) and 6.48mg of NiCl 2 Add to 30mL of deionized water and ultrasonically disperse for 30 minutes (min) to prepare mixture A. Solution B was prepared by dissolving 228mg of Ammonium Persulfate (APS) in 15mL of deionized water. Solution B was added dropwise to mixture A and stirring was continued at room temperature (25 ℃) for 4 hours. The mixture was suction-filtered with deionized water until the filtrate conductivity was less than 10. Mu.S/cm, and washed twice with absolute ethanol. The product was dried in a vacuum oven (80 ℃) for 12h.
S2, pyrolyzing, namely placing 100mg of dried powder into a quartz boat, placing the quartz boat into a tube furnace filled with nitrogen, heating to 900 ℃, preserving heat for 1 hour, and cooling to room temperature along with the furnace.
And (3) taking the obtained powder as a core, and repeating the step S1 and the step S23 times to obtain the titanium oxide carrier which is tightly and completely wrapped by the carbon layer containing nickel nitrogen. The prepared sample is marked as TiO 2 @Ni-N-C(DAP)。
Table 3. Conductivity at 20MPa for the samples prepared in the examples.
Sample name Testing pressure intensity Conductivity of
TiO 2 @Co-N-C(DAP) 20MPa 2.7×10S/cm
TiO 2 @Co-N-C (dopamine) 20MPa 2.2×10S/cm
TiO 2 @Co-N-C (aniline) 20MPa 2.2×10S/cm
Al 2 O 3 @Co-N-C(DAP) 20MPa 2.4×10S/cm
C@Co-N-C(DAP) 20MPa 3.1×10S/cm
SiC@Co-N-C(DAP) 20MPa 2.9×10S/cm
TiO 2 @Fe-N-C(DAP) 20MPa 2.3×10S/cm
TiO 2 @Ni-N-C(DAP) 20MPa 2.3×10S/cm
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (10)

1. A catalytic carrier, characterized in that the catalytic carrier takes nano carrier material as a core and doped carbon as a shell; the doped carbon contains at least one of transition metal, nitrogen, sulfur and phosphorus.
2. The catalytic carrier of claim 1, wherein the nano-carrier material comprises Al 2 O 3 Carbon, siO 2 、TiO 2 、SnO 2 、ATO、SiC、ZrO 2 Or a mixture of a plurality of the materials, or a composite nano material formed by a plurality of the materials.
3. The catalytic carrier of claim 1 wherein the transition metal is at least one of Fe, co, ni, cu.
4. The catalytic carrier of claim 1, wherein the doped carbon has a molar ratio of carbon: transition metal: nitrogen: sulfur: phosphorus = 100-30:0-20:0-30:0-10:0-10.
5. A process for preparing a catalytic support according to claim 1 to 4, comprising the steps of,
s1, coating, namely preparing a nano carrier material and a coating material, wherein the coating material comprises a carbon source and at least one of a transition metal source, a nitrogen source, a sulfur source and a phosphorus source; coating the coating material on the surface of the nano carrier material to obtain a composite material;
s2, pyrolyzing, heating the composite material to carbonize a shell layer, and obtaining the catalytic carrier.
6. The method for preparing a catalytic carrier according to claim 5, wherein the coating material is coated on the surface of the nano-carrier material in a complexing, polymerizing or adsorbing manner.
7. The method for producing a catalytic carrier according to claim 5, wherein the carbon source is a carbonaceous small organic molecule; the nitrogen source is a nitrogen-containing organic small molecule; the sulfur source is sulfur-containing organic micromolecules; the phosphorus source is a phosphorus-containing organic small molecule; the transition metal source is small organic molecules containing transition metal or inorganic transition metal salt or organic transition metal salt.
8. The method for producing a catalytic carrier according to claim 7, wherein the small organic molecule containing a transition metal comprises at least one of iron phthalocyanine, cobalt phthalocyanine, iron porphyrin, cobalt porphyrin;
the transition metal inorganic salt comprises FeCl 3 、CoCl 2 、NiCl 2 、CuCl 2 、Fe(NO 3 ) 3 、Co(NO 3 ) 2 、Ni(NO 3 ) 2 、Cu(NO 3 ) 2 At least one of (a) and (b);
the transition metal organic salt comprises at least one of ferric acetylacetonate, ferrous acetate, ferric acetate, ferrocene, cobalt acetylacetonate, cobalt acetate, nickel acetylacetonate and nickel acetate.
9. The method according to claim 7, wherein the small carbon-containing organic molecule or the small nitrogen-containing organic molecule comprises at least one of aniline, pyridine, pyrrole, 2, 6-diaminopyridine, and dopamine.
10. The method for producing a catalytic carrier according to claim 5, wherein the composite is washed and dried before step S2.
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